Oil-in-water type emulsion for flameproofing fabrics



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sfTA'Tgs PATENT orrice 7 OIL-lN-WATER TYPE EMULSION FOR 3 TFLAMEPROOFING FABRICS i Frederick Fordemwalt, Bound Brook, N. 1., as-

. v signer to American Cyanamid Company, New

York, N. Y., a corporation of Maine No Drawing. Application December 7,1949,

Serial No. 131,696 8 Claims. (01. 260-15) This invention relates to thetreatment of fabrics to produce desirable color and flame-resistantproperties therein. In particular, the invention relatesto. a newgroupof novel oil-inwater type. emulsions, and to their preparation ,and usewhereby in asingle treatment color and .jflame-resi'sting materials canbe readily deposit- 2 for use therein should be free from theobjectionable difficulties noted above and should not .result in theproduction of articles which are subject to such troubles.

It is, therefore, the principal object of the present invention toproduce a novel composition adapted to deposit the desired coloring andflameproofing materials on the fabric in a single treatment and from anaqueous medium. It is, also an object of the invention to devise atreating process which is adapted to handle a wide range of colorwithout being subject to color distortion by the flame proofing. It is astill further object ,to produce articles which have a soft, flexiblecases wholly. unsatisfactory. This has been due largely. to thenecessityfor separate and successive operations which were required because thepractice of imparting these properties involved the use of incompatiblematerials. Even successive treatments were not wholly successful becauseof the adverse effect of the flame-resistant .coatings on-the colorationand vice versa. I Because of this situation, much work has been done in-.attempts to combine --these operations jpatability of the-materialsintroduced many difflculties. On the whole, such procedures, like ;theearliers-uccessi-ve treatments, were either unsuccessfulorunsatisfactory-for one or more.

-;reasons such as: expense; alteration of the hand; limited color range;requirement 'of excessive amounts of volatile, organic solvents or asubstantially all'solvent system; physical difliculty .or firehazard'in-application; requirement of spe- .cial drying techniques;lackof light fastness;

.-lack of crock-resistance; lack of permanence of flame-resistance;inability to stand weathering; wastefulness in use or application; anddifiiculty in changing the color to be applied or in cleaning 3 Maw-ruas? .3 into fewer processing steps. Here again,-incomhand and arecapable of withstanding extended weathering without excessive loss ofeither color or flame-resistance.

In accordance with the present invention these and other objects areaccomplished by the manufacture and use of novel oil-in-water emulsions.Successful use of such materials to solve the prob- .lem completely isquite remarkable in view of the diversity of materials used, the lack ofwatersolubility of the majority of them and the fact that similarattempts using common solvents lead 1 h to many complications.

While the present invention is not primarily intended to be limited toparticular materials, certain basic ingredients are commonly foundtherein. These ingredients may be roughly grouped into four types.First, there is the question of the external medium, which in thepresent invention is aqueous and preferably thickened. Second, is agroup of flame-proofing ingredients which include suitably proportionedquantities of a properly halogenated organic material and afire-resistant, uncolored pigment potentially reactive therewith. Third,is the coloring material which in the present invention is a pigment ora group of pigments. Finally, because colored pigments have no affinityfor the fabric, a binder must be provided therefor. These are basic con--stituents'which are present whether or not addi tional components areused. In the following discussion of the use of these ingredients, the

proportions given are for the amount which will poses. However, if sodesired, other commercialg:

ly available hydrophilic colloids such as for example sodium alginate,ammonium caseinate, a carboxymethyl-cellulose and the like or variousgums such as tragacanth, karaya, locust bean and the like may be used.When other thickeners are used the amount should be such as to producean approximately similar viscosity. Because of the difference in weightsof these materials as well as their differing effect on viscosity whenin solution, the amount of hydrophilic colloid used will vary, usuallybetween about 0.1 and by weight, based on the water.

Because the principal composition is an -oilin-water type emulsion .itis often desirable although not always necessary, that the continuousphase contain dispersing and/or emulsifying agents to maintain thenecessary interfaces between the phases. Preferably these take the formof water-soluble soaps, for example, ammonium oleate, ammonium stearateand the like. For most purposes the ammonium soaps are preferable tothose of sodium or potassium. About 0.25-4.0% by weight of the emulsionof ammonium oleate, or a. corresponding amount of a chemical equivalentmay he used. As will be brought out in .the examples below, about .101.5% is a good average practice. Instead of fatty-acid soaps, othermaterials such for example as ammonium caseinate; sulfonated oils suchas sulfonated castor oil, mahogany soap and the like; and sulfatedmaterials such as the sodium salt of the sulfated higher aliphaticalcohols may be used. When such emulsifying agents are present, it isdesirable that the external medium be alkaline. This is readilyaccomplished by adding aqueous ammonia or an organic base such asmorpholine or the like. For .this reason, a good practice is to add moreammonia, or its equivalent, than is required to saponify the fatty-acidswhich are added to provide the desired amount of soap. As is shown inthe following examples, a good average practice is to u e about l.2l.'7%by weight as 28% aqueous NHiOH, or its equivalent. If a preformed soapis added, the amount of ammonia, or its equivalent base, is adjustedtherefor, providing only the amount requisite to control the pH.

These dispersing and/or emulsifying agents may be added per se to thecontinuous phase. If so, they may be conveniently added along with thehydrophilic colloid. On the other hand, it may be desirable to formthese constituents in situ. In the later case it is usually desirable toadd only the alkaline component to the water phase and to add the acidiccomponent with the dispersed phase. In this Way the two components canreact and form the desired agent during the incorporation of thedispersed phase.

Having prepared the thickened aqueous material for the continuous phase,the dispersed phases containing the halogenated organic mate rial, theflame-resistant pigrrent, the binder and the coloring pigments areprepared. -These are then added stepwise to the aqueous material andsion. For best results, so far as practical application is concerned,blending should be continued until the bulk of the dispersed material isreduced to a size of approximately 30 microns or less.

With regard to the flame-proofing ingredients, the nature of thechlorinated organic hydrocarbon used may be quite widely varied. Itshould, however, possess certain properties. In particular, it should besubstantially colorless, fire-resistant, water-insoluble, readilyavailable or ,easily prepared. Preferably it should be a fluid. However,materials which are semi-fluid, that is. of waxy consistency may be usedby adding thereto a sufficient amount of a suitable solvent thinner toimpart the requisite fluidity. Several materials are well suited for useas flame-proof ing ingredients. Chlorinated paraffin is excellent.Certain chlorinated elastomers, such as partially polymerizedchlorobutadiene (neoprene), for example, have proved to be particularlywell suited for the purpose. Other useful materials include for example,polyvinyl chloride, chlorinated naphthalene, chlorinated .tricresylphosphate and the like. Although the exact relationship is not certain,it appears that where a higher degree of chlorination is used lessmaterial is required and vice versa. Chlorinated products are those mostgenerally employed because of their availability'but use of the otherhalogens is perfectly feasible. Amounts varying from 5-30% of 40%chlorinated paraflin or its equivalent may be used. As the exampleswhich follow show, a good general practice is to add enough chlorinatedmaterial to provide about 340% by weight of the padding bathas combinedchlorine, available fol-liberation of HCl at elevated temperatures.

Similarly, the fiame-resistant pigment may be varied if so desired. Itshould, however, be one which not only is compatible with the emulsionbut also is colorless or white or only lightly colored so as not toeflect adversely the coloration obtained from the color-producingmaterials. Finally, it must be one which when used with the halogenatedmaterial is effective to impart flame-resistance. Such pigments ascalcium or magnesium carbonate or the like have been used. Othersuggestions include zinc borate. magnesium ammonium phosphate, melaminepyrophosphates and the like. However, finely powdered antimony oxide hasproved generally superior in use and is therefore preferred. From about55-30% of antimony oxide or its equivalent maybe used. It has beenfound, as the examples show, that in using antimony oxide it shouldcomprise about 820% of the emulsion weigh-t Some adjustment fordiffering molecular weights of substitutes therefor may be required.

These flame-proofing materials are usually compounded into the finalemulsion as a unit by first blending together the chlorinated materialand the pigment. In so doing, a small amount of a volatile solvent,usually a hydrocar; bon solvent, is used to thin the chlorinated material slightly. Where the emulsifying agent is formed in situ it iswell to add at least part of the acidic constituent therefor with theflameproofing material. A small amount of some soapforming acidicmaterial such as linseed-oil fatty acids, oleic acid or the like, alsois added therewith in such cases. Only a sufficient amount of solventshould be used to impart the requisite fluidit since the principalpurpose of this operasyn-kit? rolle'r'mill or the equivalent.

"tion is to assist in the eventual compounding of the final emulsion andexcessive amounts of volathe solvents are neither necessary nordesirable. Since the coloring pigments have no afilnity for the fabrics,it is necessary to provide some binder to effect a pigment-fibreattachment bond. Again the invention has the advantage of notbeinglimited to specific materials. While the binders may be varied they aresubject to certain :limitations. Because color is important, the bindershould be substantially colorless or of a 'light shade. It should beunconverted, stable against conversion in the emulsion at'normaltemperatures and capable of deposition with the pigment from theemulsion. If the fabric has had some pretreatment the binder must be onecompatible with any residual material therefrom. Preferably, too,itshould be easily converted to a water-insoluble form withoutanyappreciable heating beyond that required in drying the fabric to whichthe emulsion has been applied.

In accordance with the present invention, it has been found that manyheat-convertible alkyd resins, particularl drying-oil-modified alkydsare well suited for this purpose as are many amide-aldehyde resins,particularly the alkylated resins such as butylated urea-formaldehyderesin or butylated melamine-formaldehyde resin. Preferably, in order toinsure binding while maintaining the optimum flexibility in the finishedproduct, a mixture as of oil-modified alkyd jand amide-aldehyde resinsis used. As little as "0.5 to as much as of binder resins may be fused.As illustrated in the examples below, a good practice consists of usingabout Lil-1.5% of lthe weight of the emulsion as an amide-aldehyde resinand about 2.0-3.0% as an alkyd resin, the

' total amount of resin present being from about 3-5%;

Since the flame-proofing is not the sole object but rather one of theprincipal objects, imparting color to the emulsion, and to the productstreated therewith, is an important feature. In accord- ;ance with thepresent invention, color is added to the emulsion and eventually app iedto the fabric as a finely-divided pigment. Not only does this have theadvantage of providing light fast- 'ness in a wide range of colors butit obtains this advantage without the necessity for the variousprocessing treatments required when coloring is *done by a dyeing.Substantially any solid, finelydivided, colored, light-fast pigment maybe used -if so desired. 4 It is probably preferable though not necessary-that the coloring pigments be pre-combined with the binding resins asan ink or color paste before bei'ng b ended into the final emulsion.This may "be readily accomplished by treating a mixture of thecomponents in a mixer or on a suitable ink Again, as in blendingthefiame-resisting materials,to assist in forming the emulsifying agent,a small quantity of an 'acidic soap-forming material such as a fattyacid .Jisadded. A basic soap-forming constituent such :as a small amountof aqueous ammonia also may "be added if so desired to supplement thatin the ."external phase. Further, this may be supple- .mented as desiredby additional emulsifying "and/or dispersing agents such as pineoil,terpineol,

terpenes and the like, if so desired.

..It will be seen, therefore, that the principal feature of the presentinvention is an oil-in-water etype emulsion in which external aqueousmedium is usually thickened somewhat to increase its viscosity andassist in maintaining permanent dis- While the emulsion as a whole issubstantially a stable heterogeneous composition, it does not consistsolely of water as the single dispersion medium with a number ofindividual ingredients separately suspended therein. Rather, there arepresent one or more dissolved or colloidally suspended ingredients inthe water, which solution. forms the continuous or outer phase. Inaddition, there are suspended therein at least two separate dispersedphases; one of these contains flame-proofing constituents, i. e., thefire-retarding pigments and the chlorinated hydrocarbon; .the othercontains thecoloring ingredients and the binder or binders. Each of thedispersed phases in and of itself may comprise a continuous phase havingdispersed therein one or more ingredients. Each may, if necessary,contain separate agents to maintain the necessary interfaces.

The above appears to be the principal nature of the final emulsion. Thisis a consequence of the manner in which the emulsion is compounded. Thusthe aqueous dispersion medium is first formulated and then there areseparately dis- .persed therein, first the blend containing thename-proofing ingredients, and second, the blend containing the binderor binders with or without color. There is, of course, a possibilitythat part of the material, notably from the pigment and binder blend, isnot retained within individual droplets which droplets are dispersed inthe medium. Rather, a part of the material may migrate from the dropletsand be dispersed per se in the aqueous medium. Some such variation isusually found in all such compositions and does not alter the generalcharacteristics of the composition as a heterogeneous oil-in-wateremulsion. The invention is not necessarily limited to the treatment ofany particular materials. Its primary intention is for the treatment oftextile fabric sheets and the discussion has been primarily concernedtherewith. However, the emulsion is equal y well-adapted to thetreatment of yarn either in running lengths or skeins. It is capable ofproducing effective coatings of paper. Metallic fabrics may be alsoeffectively treated; but in the latter case, it is desirable to increasethe binder content in order to do so. Treatment of such materials ishowever, of little practical importance except for wire reinforcedfabrics since the flame-proofing feature is not required in work inwhich only metallic fabrics are used. The invention will be moreillustrated in conjunction with the following examples which areintended by way of illustration only, but not by way of limitation. Allparts are by weight unless otherwise noted.

l ExampleI Ajstable, oil-in-water type of emulsion to serve as the basisof the mix was prepared by the foland 970 parts of water were added andthe whole 'zgssegevaa Z biend'e'd to uniformity; To this was added: apre viousliy'blended' mixture-of 400 parts: of chlorinatedf parafiin(40-45% chlorineby weight-)1, 400' parts of. antimony oxide;v (325mesh); 100 parts of hydrocarbon solvent (distillation range 135-1-7-5"C; and containing 92% aromatics) and. parts ofilinseed oilfatty'acids. When admixture: was complete, stirring was continued untilthe: emulsionbecame smooth;

Simuitaneouslythere-was prepared by mechanical stirring a pigmented mixcomprising 220 parts of finely' ground chromium oxide, 91.5 partsof a:70% solution of an alkyd resin in apine oil solvent (the alkyd resinbeing prepared by condensing 148 parts of phthalic' anhydride; 97. partsof glycerine, 182 parts of soya-bean fattyacids and 53 parts of castoroil, condensation being carried out at approximately 210-250? C: untiltheacid' number is between 3 and 7 32 parts of a=5.0% solution ofbutylated' ureafbrmaldehyde resin in asolvent comprising equal parts ofxylol and butanol, (the resin'being pre'-- pared by refluxingdimethylolureawith excess butanol), lost-parts of'pine oil, parts ofoleic.

acid, and 20 parts of'aqueous ammonia (specific gravity 0.90). Thismixture was milled together on athree roller ink millwith tightlyadjusted V rollers;

The aqueous emulsion and the pigmented mix were blendedto uniformconsistency Icy-mechanical stirring to produce a smooth pigmented oil'-in-water typeemulsion. Thisemulsion was employed by padding ontoburlapand Osnaburg fabri'csand squeezing the padded fabric" to a wet weightincrease ofabout 100% of the original dry weight and then completelydrying the treated fabrics. The treated fabrics remained soft andflexiblecomparin'g fairlyin' these properties to the untreated material.The appearance was'completely uniform and the fabrics possessed anotabl'y' high degree of flameresistance. Continued exposure tosevere-weathering conditions such as to six months outdoor-exposure orthe equivalent hours in an Atlas 'dual-arc weatheromet'erdid not destroythese properties. The above example corresponds to thefollowingformulation:

l C ompoucnt Z% Methyl Cellulose 0. 21 28% A ueousAmmon 1:66 Fatty cidsllll l l l.

(1. 33). Antimony Oxide. 16.60 Cbl l 40% Chlorine s 1d 60' (42=l:l%realChlorine). (6184.15) Hydrocarbon Solvent c 4. 15 no 0" 1.80 l-tlloydresin 2. G6 50% Uroal orm dehydc B 1.33 Pigment-Chromium Oxide- 9.10Water 44.134.

Example.- 2

A basic emulsion was prepared identical with that of Example 1 exceptthat the chlorinated paraffin content was altered to 268 parts ofchlorinat'ed parafiln containing approximately 60% of combined chlorinedissolved in 132 parts of the hydrocarbon solvent described in ExampleI. At the same time, a pigmented mix was prepared es-in Example 1 from220 parts of chromium oxidepigment; 91.6 parts of the 70% alkyd resinsolution of Example I, 32 parts of the-50% solution of' butylated ureaformaldehyde resin described in Exampie- 1', IGA parts of. pine 011;" 20parts of oleic acid, and 20 parts of aqueous ammonia (sp. gr. 0.90). Theemulsion and pigment mix were mechanically: blended to uniformconsistency and as in Example 1 the result was a smooth oil-in-wate typeemulsion used. in padding burlap and Osnaburg fabrics. As in Example '1,a smooth uniform color and high flame resist ance were obtained withoutsubstantially altering the hand and these desirable propertiesremaindespite continued exposure to severe weather. The above examplecorresponds to the following formulation:

Example" 3 l 183; parts of. a. 20 solution. of. anelastomericchlorobutadiene polymer in a hydrocarbon solvent (boiling at l-35-l7.5C. and containing 92% aromatichydrocarbons) were mixed with '73 parts ofpulverized antimony oxide (325 mesh), 5 parts of the dried andpulverized precipitate obtained by adding an. acidified solution ofsodiumpyrophosphate to a boiling solution of melamine, 29 parts ofchlorinated paraffincontaining 72% combined chlorine, 1.8'- parts of.oleic acid, and.55. parts. of hydrocarbonsolvent (boiling at. l35-175 C.and containing 92% aromatics) Tfis mix was added, withcontinuousagitation, toa uniform. aqueous solution of 3.6 parts ofmethyl cellulose (3,000 centipoise Methocel). 5 parts of 28% aqueousammonia and 385 partsof water and the agitation continued to. form. asmooth oil-in-water type emulsion.

Simultaneously therewasprepared by mechanical stirring a pigmented mixcomprising 10 parts of yellow precipitated iron oxide pigment, 25- partsof the alkyd resin solution described in Example 1, 8 partsof thebutylatedurea formaldehyderesin solution described in Example 1, 5 partsof pine oil, 5 parts of oleic' acid, and 6 parts of aqueous ammonia (sp;g. 0.90). This mixture was milled together on a; three roller. ink. millwith. tightly adjusted. rollers.

The aqueous emulsion and the pigmented mix wereblended to uniformconsistency by mechanical stirring to produce a smooth pigmentedoilin-water type emulsion. This emulsionwas, emeployed by padding ontoburlap and Osnaburg fabrics and squeezing the padded. fabric. to. a. wetweight increase of about offthe original dry weight and then completelydrying the treated fabrics. The treated; fabrics remained soft andflexible comparing fairly in these properties to" the untreatedmaterial. The appearance was com.- pletely'uniform and the fabricspossessed. anotably high degree of flame-resistance. Continued exposureto severe weathering conditions suciras to six-monthsoutdcor exposure-orthe.- equivalent hours in -an Atlas dual-arc weatherometerdidnot once-odestroy these properties. The above example corresponds to the followingformulation:

Component g g Methyl Cellulose 0. 45 28% Aqueous Ammonia .1 1. 37 FattyAcids 0. 98

(As Ammonium Soap) (1. 04) Antimony Oxide 9.14

Chlorinated Paraffin:

72% Chlorine 3. 62 +Chlorobutadiene 4. 57 Hydrocarbon Solvent 25.10Melamine gyropl gsphate 0.63 me i 1. 56 Alkyd Resin 2.19 50% UreaFormaldehyde Resin 1.00 Pigment-Iron Oxide l. 25 Water 48.14

I claim:

1. A stable, heterogeneous, oil-in-water type emulsion, adapted for thesimultaneous deposition on fabrics from an aqueous medium offireresisting, coloring and binding materials, which emulsion iscomprised of a continuous dispersion medium comprising water containinga hydrophilic colloid; a dispersed phase comprising a film-forming,substantially colorless fire-resistant, water-insoluble, non-volatile,chlorinated organic compound capable of liberating HCl at elevatedtemperatures, a colorless, fire-retarding pigment, and a hydrocarbonsolvent; a separately dispersed phase comprising water-insoluble organicsolvent, at least one coloring pigment and an uncured, heat-convertible,binder resin, selected from the group consisting of (a) thedrying-oil-modified alkyd resins, (b) the organic hydrocarbonsolvent-soluble, amide-aldehyde resins and mixtures thereof; and awatersoluble soap of a higher fatty acid, the proportions as weightpercentages of the total emulsion being 01-10% hydrophilic colloid,sufficient chlorinated organic compound to provide from about 2-12% ofcombined chlorine capable of liberating HCl at elevated temperatures,5-30% fire-retarding pigment, 05-10% binder resin and 0.25-4.0% soap.

2. A composition according to claim 1 in which the hydrophilic colloidis a water-soluble methyl cellulose and the emulsifying agent is anammonium soap.

3. A composition according to claim 1 in which the dispersed material issubstantially all dispersed in sizes not greater than 30 microns.

4. A stable, heterogeneous, oil-in-water-type emulsion, adapted for thesimultaneous deposition on fabrics from an aqueous medium offireresisting, coloring, and binding materials, which emulsion iscomprised of a continuous dispersion medium comprising water containinga hydrophilic colloid; a dispersed phase comprising a film-forming,non-volatile, chlorinated parafiin, finely-divided antimony oxide and ahydrocarbon solvent; a separately dispersed phase comprisingwater-insoluble organic solvent, at least one coloring pigment and anuncured, heat-convertible, binder resin selected from the groupconsisting of (a) the drying-oil-modifled alkyd resins, (b) the organichydrocarbon solventsoluble amide-aldehyde resins, and (0) mixturesthereof; and a water-soluble soap of a higher fatty acid, theproportions as weight percentages of the total emulsion being 01-10%hydrophilic colloid, sufficient chlorinated paraffin to provide fromabout 2-12% of combined chlorine capable of liberating HCl at elevatedtemperatures, 5-30 antimony oxide, 05-10% binder resin and 0.25-4.0%soap.

5. A method of producing a stable, heterogeneous, oil-in-water-typeemulsion, adapted for the simultaneous deposition on fabrics from anaqueous medium of fire-resisting, coloring, and binding materials, whichcomprises the steps of preparing an aqueous medium by dissolving therein01-10% of a hydrophilic colloid, 0.25-4.0% of a water-soluble soap of ahigher fatty acid and sufiicient alkaline material to maintain analkaline pH; blending into a smooth paste a mixture comprisingsuflicient film-forming, substantially colorless, fire-resistant,waterinsoluble, non-volatile, chlorinated organic compound to providefrom about 2-12% of combined chlorine capable of liberating HCl atelevated temperatures, 5-30% of a colorless fire-retarding pigment andonly a sufficient amount of a hydrocarbon solvent to impart fluidity;blending at least one coloring pigment into a smooth paste with asolvent solution of 05-10% of an uncured, heat-convertible binder resin,selected from the group consisting of (a) the drying-oil-modified alkydresins, (b) the organic hydrocarbon solvent-soluble amide-aldehyderesins and (0) mixtures thereof, and separately dispersing the pastedmaterials into the aqueous medium, the percentages given being weightpercentages of the total emulsion.

6. A process according to claim 5 in which the hydrophilic colloid is awater-soluble methyl cellulose and the emulsifying agent is an ammoniumsoap.

7. A process according to claim 5 in which the dispersed material issubstantially all dispersed in sizes not greater than ,30 microns.

8. A process according to claim 5 in which the emulsifying agent is anammonium soap of a higher fatty acid formed in situ by adding the acidiccomponent to the aqueous medium and adding the basic constituent withthe dispersed phase.

FREDERICK FORDEMWALT.

REFERENCES CITED The following references are of record in the file ofthis patent:

, UNITED STATES PATENTS Number OTHER REFERENCES Chemical Industries,article by Scheer, vol. 54, No. 2, Feb. 1944. DD. 203-205.

Btiiiiliii l'iUUil

1. A STABLE, HETEROGENEOUS, OIL-IN-WATER TYPE EMULSION, ADAPTED FOR THESIMULTANEOUS DEPOSITION ON FABRICS FROM AN AQUEOUS MEDIUM OFFIRERESISTING, COLORING AND BINDING MATERIALS, WHICH EMULSION ISCOMPRISED OF A CONTINUOUS DISPERSION MEDIUM COMPRISING WATER CONTAININGA HYDROPHILIC COLLOID; A DISPERSED PHASE COMPRISING A FILM-FORMING,SUBSTANTIALLY COLORLESS FIRE-RESISTANT, WATER-INSOLUBLE, NON-VOLATILE,CHLORINATED ORGANIC COMPOUND CAPABLE OF LIBERATING HC1 AT ELEVATEDTEMPERATURE, A COLORLESS, FIRE-RETARDING PIGMENT, AND A HYDROCARBONSOLVENT; A SEPARATELY DISPERSED PHASE COMPRISING WATER-INSOLUBLE ORGANICSOLVENT, AT LEAST ONE COLORING PIGMENT AND AN UNCURED, HEAT-CONVERTIBLE,BINDER RESIN, SELECTED FROM THE GROUP CONSISTING OF (A) THEDRYING-OIL-MODIFIED ALKYD RESINS, (B) THE ORGANIC HYDROCARBONSOLVENT-SOLUBLE, AMIDE-ALDEHYDE RESINS AND (C) MIXTURES THEREOF; AND AWATERSOLUBLE SOAP OF A HIGHER FATTY ACID, THE PROPORTIONS AS WEIGHTPERCENTAGES OF THE TOTAL EMULSION BEING 0.1-10% HYDROPHILIC COLLOID,SUFFICIENT CHLORINATED ORGANIC COMPOUND TO PROVIDE FROM ABOUT 2-12% OFCOMBINED CHLORINE CAPABLE OF LIBERATING HC1 AT ELEVATED TEMPERATURES,5-30% FIRE-RETARDING PIGMENT, 0.5-10% BINDER RESIN AND 0.25-4.0% SOAP.